CN1272852A - Process for preparation of copolymers of ethylene with alpha-olefins - Google Patents

Process for preparation of copolymers of ethylene with alpha-olefins Download PDF

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CN1272852A
CN1272852A CN99800985A CN99800985A CN1272852A CN 1272852 A CN1272852 A CN 1272852A CN 99800985 A CN99800985 A CN 99800985A CN 99800985 A CN99800985 A CN 99800985A CN 1272852 A CN1272852 A CN 1272852A
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alkyl
dichloride
substituent
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aluminium
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T·达尔奥科
L·雷斯科尼
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Spherilene SRL
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

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Abstract

Ethylene based copolymers having high molecular weights, narrow molecular weight distributions, and a very good homogeneous distribution of the comonomer units can be obtained in high yields at temperatures of industrial interest, by carrying out the polymerization reaction in the presence of metallocene catalysts comprising particular bridged bis-indenyl compounds substituted in the 3-position on the indenyl groups.

Description

The preparation method of ethene and alpha-olefin copolymer
The present invention relates to the preparation method of ethene and alpha-olefin copolymer.
Be known as the catalyst component of the homopolymerization and the copolyreaction of alkene with the metallocene complex of two bridged ring pentadienyls.
For example, U.S. Patent No. 5,001,205 disclose in the presence of catalyst system, the preparation of ethene and alpha-olefin copolymer, this catalyst system comprise the bicyclic pentadiene title complex of zirconium, titanium and hafnium and as the methyl oxidation aluminum alkyls (methylalumoxane) of promotor (MAO).Embodiment disclose bridging or not bridging dichloride (tetrahydroindene) close zirconium in the presence of the copolymerization of ethene and propylene.
Although the multipolymer that is obtained by traditional titanium base and vanadium base ziegler-natta type catalyzer has improved the homogeneity that alpha-olefin distributes on the chain, it still is not satisfactory especially, still presses for further improvement.
Also known metallocene complex with two acyclic isoprenoid parts of monatomic bridging.For example, PCT application WO 96/22995 discloses by the metallocene complex of single carbon atom bridging and they in olefinic polymerization, especially in the propylene polymerization as Application of Catalyst.Shown that the metallocene complex kind that is specially adapted to propylene polymerization is two indenes classes of single carbon atom bridging, wherein the indenes part replaces for carbon, silicon or germanium atom with three hydrocarbon substituents on 3 positions.But the example of delivering that had not both had ethene and alpha-olefin copolymer to close does not have any information of relevant gained ethylene copolymer performance to provide yet.Especially, the data that does not have relevant comonomer to distribute along polymer chain.
The catalyzer that selection can be produced the ethylene copolymer of the distributing homogeneity with improved comonomer unit along polymer chain is desirable.Now be surprised to find that, comprising the special polyreaction of in the presence of the metallocene catalyst of two indenyl title complexs of substituted monatomic bridging on indenyl 3 positions, carrying out ethene, it is possible based on the multipolymer of ethene that preparation has high-molecular weight, in this multipolymer, the distribution of comonomer is extremely even on the polymer chain, and operates under the interested temperature of industry member.
Therefore, according to first aspect, the invention provides a kind of method for preparing ethylene copolymer, this method is included in catalyzer and has ethene and the polyreaction that is selected from least a comonomer in alpha-olefin, cyclenes and the polyenoid down, and this catalyzer comprises by (A) and contacts resultant product with (B): (A) general formula is the metallocene complex of (I):
Figure A9980098500061
Wherein:
Substituent R 1Be hydrogen atom or C 1-C 20Alkyl;
Substituent R 2Be CHR 10R 11, SiR 12R 13R 14Or GeR 15R 16R 17Group,
Wherein: R 10, R 11, R 12, R 15Be hydrogen atom, C 1-C 20Alkyl, C 3-C 20Cycloalkyl, C 2-C 20Alkenyl, C 6-C 20Aryl, C 7-C 20Alkaryl or C 7-C 20Arylalkyl radical, optional Siliciumatom or the germanium atom of comprising;
R 13, R 14, R 16, R 17Be C 1-C 20Alkyl, C 3-C 20Cycloalkyl, C 2-C 20Alkenyl, C 6-C 20Aryl, C 7-C 20Alkaryl or C 7-C 20Arylalkyl radical, optional Siliciumatom or the germanium atom of comprising;
R 3And R 4, identical or different, be hydrogen atom or-CHR 5R 6Group;
R 3And R 4Can form and to contain heteroatomic, as to have 3-8 carbon atom ring;
R 5And R 6, identical or different, be hydrogen atom, C 1-C 20Alkyl, C 3-C 20Cycloalkyl, C 2-C 20Alkenyl, C 6-C 20Aryl, C 7-C 20Alkaryl or C 7-C 20Arylalkyl radical, it can form can contain heteroatomic, as to have 3-8 carbon atom ring;
R 7Substituting group, identical or different, be C 1-C 20Alkyl, C 3-C 20Cycloalkyl, C 2-C 20Alkenyl, C 6-C 20Aryl, C 7-C 20Alkaryl or C 7-C 20Arylalkyl radical, optional silicon or the germanium atom of comprising; And optional two adjacent R 7Substituting group can form the ring that comprises 5-8 carbon atom, and n is the integer of 0-4;
M is selected from that those belong to 3,4 in the periodic table of elements (IUPAC redaction), the transition metal atoms of 5,6 families or group of the lanthanides or actinium series, and X, identical or different, be the single anion ligand, such as hydrogen atom, halogen atom, R 8, OR 8, OSO 2CF 3, OCOR 8, SR 8, NR 8 2Or PR 8 2Base, wherein, substituent R 8Be C 1-C 20Alkyl, C 3-C 20Cycloalkyl, C 2-C 20Alkenyl, C 6-C 20Aryl, C 7-C 20Alkaryl or C 7-C 20Arylalkyl radical, optional Siliciumatom or the germanium atom of comprising; P is the integer of 0-3, and the oxidation state that equals metal M deducts 2; And
(B) can form the oxidation of alkyl aluminium (alumoxane) and/or the title complex of alkyl metallocene cation.
Transition metal M preferentially is selected from titanium, zirconium and hafnium.
Preferred chlorine atom of X substituting group or methyl.
R1 and the preferred hydrogen atom of R7 substituting group.
The example that is applicable to the unrestriced metallocene complex of the inventive method is:
Dichloride and dimethylated methylene base-two (3-methyl-indenyls) close zirconium;
Dichloride and dimethyl isopropylidene-two (3-methyl-indenyls) close zirconium;
Dichloride and dimethylated methylene base-two (3-ethyl-indenyls) close zirconium;
Dichloride and dimethyl isopropylidene-two (3-ethyl-indenyls) close zirconium;
Dichloride and dimethylated methylene base-two (3-dimetylsilyl-indenyls) close zirconium;
Dichloride and dimethyl isopropylidene-two (3-dimetylsilyl-indenyls) close zirconium;
Dichloride and dimethylated methylene base-two (3-dimethyl germyl-indenyls) close zirconium;
Dichloride and dimethyl isopropylidene-two (3-dimethyl germyl-indenyls) close zirconium;
Dichloride and dimethylated methylene base-two (3-trimethyl silyl-indenyls) close zirconium;
Dichloride and dimethyl isopropylidene-two (3-trimethyl silyl-indenyls) close zirconium;
Dichloride and dimethylated methylene base-two (3-triethylsilyl-indenyls) close zirconium;
Dichloride and dimethyl isopropylidene-two (3-triethylsilyl-indenyls) close zirconium;
Dichloride and dimethylated methylene base-two (3-trimethylammonium germyl-indenyls) close zirconium;
Dichloride and dimethyl isopropylidene-two (3-trimethylammonium germyl-indenyls) close zirconium;
Dichloride and dimethylated methylene base-two (3-diphenylmethyl silylation-indenyls) close zirconium;
Dichloride and dimethyl isopropylidene-two (3-diphenylmethyl silylation-indenyls) close zirconium;
Dichloride and dimethylated methylene base-two (3-diethylsilane base-indenyls) close zirconium;
Dichloride and dimethyl isopropylidene-two (3-diethylsilane base-indenyls) close zirconium;
Dichloride and dimethylated methylene base-two (2-methyl-3-trimethyl silyl-indenyl) close zirconium;
Dichloride and dimethyl isopropylidene-two (2-methyl-3-trimethyl silyl-indenyl) close zirconium;
Dichloride and dimethylated methylene base-two (2-methyl-3-diethylsilane base-indenyl) close zirconium;
Dichloride and dimethyl isopropylidene-two (2-methyl-3-diethylsilane base-indenyl) close zirconium;
Dichloride and dimethylated methylene base-two (3-benzyl silyl-indenyls) close zirconium;
Dichloride and dimethyl isopropylidene-two (3-benzyl silyl-indenyls) close zirconium;
Dichloride and dimethylated methylene base-two (3-cyclopentyl silyl-indenyls) close zirconium;
Dichloride and dimethyl isopropylidene-two (3-cyclopentyl silyl-indenyls) close zirconium;
Dichloride and dimethylated methylene base-two (2-ethyls-3-diethylsilane base-indenyl) close zirconium;
Dichloride and dimethyl isopropylidene-two (2-ethyls-3-diethylsilane base-indenyl) close zirconium.
At general formula is in the metallocene complex of (I), R 2Be CHR 10R 11Base, preferred R 10It or not hydrogen atom.More preferably, R 10And R 11It not hydrogen atom.
The interested especially general formula that is used for the inventive method is that the metallocene complex of (I) is those R therein 1Be hydrogen atom and R 2Be CHR 10R 11The group person.
The non-limitative example that belongs to this type of is:
Dichloride and dimethylated methylene base-two (3-sec.-propyl-indenyls) close zirconium; Dichloride and dimethyl isopropylidene-two (3-sec.-propyl-indenyls) close zirconium; Dichloride and dimethylated methylene base-two (3-isobutyl--indenyls) close zirconium; Dichloride and dimethyl isopropylidene-two (3-isobutyl--indenyls) close zirconium; Dichloride and dimethylated methylene base-two (3-isopentyl-indenyls) close zirconium; Dichloride and dimethyl isopropylidene-two (3-isopentyl-indenyls) close zirconium; Dichloride and dimethylated methylene base-two (3-diphenyl-methyl-indenyls) close zirconium; Dichloride and dimethyl isopropylidene-two (3-diphenyl-methyl-indenyls) close zirconium; Dichloride and dimethylated methylene base-two (3-dicyclohexyl methyl-indenyls) close zirconium; Dichloride and dimethyl isopropylidene-two (3-dicyclohexyl methyl-indenyls) close zirconium.The most preferred metallocene complex of general formula (I) is that dichloride methylene radical-two (3-sec.-propyl-indenyls) close zirconium and dichloride isopropylidene-two (3-sec.-propyl-indenyls) close zirconium.
General formula be (I) metallocene complex can by corresponding indenyl ligands with can on cyclopentadienyl rings, form the anionic compound of delocalization, and and general formula be MX P+2The compound prepared in reaction, M wherein, X and p such as above-mentioned definition.
The ligand of general formula (I) can prepare by diverse ways.A kind of method that is particularly suitable for preparing the ligand of general formula (I), wherein R 3And R 4Be hydrogen atom, be disclosed in the European Patent Application No. 97200933.6 with the name of same Applicant.A kind of method that is particularly suitable for preparing the ligand of general formula (I), wherein substituent R 3And R 4Not hydrogen atom, be disclosed in European Patent Application No. 0 722 949.Be different under the situation of halogen at least one substituent X in the metallocene complex of (I) at the general formula that will prepare, must replace at least one substituent X in the metallocene that obtains with at least one substituent X that is different from halogen.The reaction that replaces substituent X with the substituent X that is different from halogen adopts common application method to carry out.For example, if needed substituent X is an alkyl, metallocene can by with magnesium alkyl halide (Ge Liya reagent) or alkyl lithium compounds prepared in reaction.
Be used for the catalyzer of the method according to this invention, general formula can both be AIR as general formula for the metallocene complex and the oxidation of alkyl aluminium of (I) 9 3Or general formula is Al 2R 9 6The reaction product of organo-metallic aluminum compound have R wherein 9Substituting group, identical or different, its definition is the same with substituent R, or hydrogen atom.The oxidation of alkyl aluminium that uses in the methods of the invention can be by being AlR with water and general formula 9 3Or Al 2R 9 6The organo-metallic aluminum compound contact and obtain, R wherein 9Substituting group, identical or different, as above-mentioned definition, condition is at least one R 9Be different from halogen.Mol ratio between aluminium and the water is 1: 1-100: 1 scope.
General formula is AlR 9 3Or Al 2R 9 6The example of nonrestrictive aluminum compound be: Al (Me) 3, Al (Et) 3, AlH (Et) 2, Al (iBu) 3, AlH (iBu) 2, Al (iHex) 3, Al (iOct) 3, AlH (iOct) 2, Al (C 6H 5) 3, Al (CH 2C 6H 5) 3, Al (CH 2CMe 3) 3, Al (CH 2SiMe 3) 3, Al (Me) 2IBu, Al (Me) 2Et, AlMe (Et) 2, AlMe (iBu) 2, Al (CH 2-CH (Me) CH (Me) 2) 3, Al (Me) 2IBu, Al (Me) 2Cl, Al (Et) 2Cl, AlEtCl 2AndAl 2(Et) 3Cl 3,
Wherein, Me=methyl, Et=ethyl, iBu=isobutyl-, iHex=isohexyl, iOct=2,4,4-trimethylammonium-amyl group.
In above-mentioned aluminum compound, preferred trimethyl aluminium (TMA), triisobutyl aluminium (TIBAL) and three (2,4,4-trimethylammonium-amyl group) aluminium (TIOA).
Think that the oxidation of alkyl aluminium that is used for catalyst according to the invention is linear, branching or cyclic compound, comprises at least one group of following type:
Substituent R wherein 18, identical or different, be C 1-C 20Alkyl, C 3-C 20Cycloalkyl, C 2-C 20Alkenyl, C 6-C 20Aryl, C 7-C 20Alkaryl or C 7-C 20Arylalkyl radical, optional hydrogen atom, Siliciumatom or the germanium atom of comprising, or-O-Al (R 18) 2Group, if desired, the part substituent R 18It can be halogen atom.
Especially, the oxidation of alkyl aluminium of following general formula:
Figure A9980098500102
Can be used under the situation of ol cpds, wherein n is 0 or integer and the substituent R of 1-40 18Be definition as mentioned above; Or the oxidation of alkyl aluminium of following general formula:
Can be used under the situation of ring compound, wherein n is integer and the substituent R of 2-40 18Be definition as mentioned above.
Substituent R 18Preferred ethyl, isobutyl-or 2,4,4-trimethylammonium-pentyl group.
The example that is fit to the oxidation of alkyl aluminium of use according to the present invention is methyl oxidation aluminum alkyls (MAO), isobutyl-oxidation of alkyl aluminium (TIBAO), 2,4,4-trimethylammonium-amyl group oxidation of alkyl aluminium (TIOAO) and 2,3-dimethylbutyl oxidation of alkyl aluminium.
Mol ratio between the atoms metal of aluminium and metallocene complex is generally 10: 1 to 20000: 1, preferred 100: 1 to 5000: 1.The example that can form the non-limiting compound of alkyl metallocene cation is that general formula is Y +Z -Compound, Y wherein +Be protonic acid, can supply with a proton and with general formula (I) in the substituent X generation irreversible reaction of metallocene; Z -Be compatible negatively charged ion, this negatively charged ion does not have coordination, and can stablize the active catalyst form that is produced by two kinds of compound reactions, and this anionic unstable is enough to remove from Olefins matrix.Preferably, negatively charged ion Z-is made up of one or more boron atoms.More preferably, negatively charged ion Z -Be Formula B Ar 4 (-)Negatively charged ion, substituent A r wherein, it can be identical or different, is such as aryl such as phenyl, pentafluorophenyl group or two (trifluoromethyl) phenyl.Especially preferred boric acid four (penta fluoro benzene) ester.In addition, can use general formula to be BAr usually 3Compound.This compounds is disclosed in, such as, the International Patent Application WO of delivering 92/00333, its content is incorporated in this explanation.
Catalyzer of the present invention also can use on carrier.This product by metallocene complex (A) or it and component (B) are reacted, or first component (B) is reached is deposited on following carrier with metallocene complex (A) again, such as, obtain on silicon-dioxide, aluminum oxide, magnesium halide, vinylbenzene/divinylbenzene copolymer, polyethylene and the polypropylene.
The kind of carrier that is fit to that can use is those porous organic carriers by the radical functino of band reactive hydrogen atom.Particularly suitable is that those organic carriers are partial cross-linked styrene polymer.Such carrier is disclosed in European application EP-663 272.
According to the present invention, the inert support of another kind of particularly suitable is disclosed in the International Application No. WO 95/26369, and it is alkene porous prepolymer, particularly propylene.
According to the present invention, the inert support that a class is suitable for more is a porous magnesium halide class, for example is disclosed in the International Application No. WO 95/32995 those.The solid chemical compound of gained with the combination of the alkylaluminium cpd of further interpolation, or directly adds or reacts in advance with water if desired, can adopt in vapour phase polymerization.
In the presence of above-mentioned special metallocene complex, the polymerization of ethene and alpha-olefin, can be under the interested temperature of industry member (promptly, be higher than 50 ℃), obtain high yield, obtain the extremely uniform ethylene copolymer of comonomer distribution in polymer chain, that is, two or more alpha-olefin derived unitary sequential cells sequence numbers are very low.In multipolymer of the present invention, the analysis that alpha-olefin distributes is adopted 13The C-NMR wave spectrum carries out.This mensuration under ethene/1-hexene copolymer situation, is disclosed in " polymer chemistry physics (Macromol.Chem.Phys.) " (1989) by J.C.Randall, and 29,201 method is carried out.
According to olefine polymerizing process of the present invention, can under inert hydrocarbon solvent existence or non-existent situation, in liquid phase, carry out, or in gas phase, carry out.Varsol can be aromatic series such as toluene, or aliphatics such as propane, hexane, heptane, Trimethylmethane or hexanaphthene.
Polymerization temperature is generally-100 ℃-+100 ℃, and is in particular 10 ℃-+90 ℃.Polymerization pressure is generally the 0.5-100 crust.
Polymerization temperature is low more, and the final molecular weight of resulting polymers is high more.
Polymerization yield rate depends on the purity of metallocene in the catalyzer.So the metallocene complex that is obtained by method of the present invention can directly use, or through purification process.
The component of catalyzer can be in contact with one another before polymerization.Pre-exposure concentration is 1-10 concerning metallocene complex (A) -8Mol/L is 10-10 concerning component (B) -8The pre-contact of mol/L usually varsol and, if desired, small amounts of monomer is carried out under existing.In pre-contact, also can use the alkene of non-gathering property, as iso-butylene, 2-butylene etc.
In the multipolymer that adopts method of the present invention to obtain, the molar content of ethylene-derived units is preferably 80%-99% usually above 50%.
Alpha-olefin derived unitary molar content is preferably 0%-50%, more preferably 1%-20%.
The content of polyene hydrocarbon derived units is preferably 0%-4%, more preferably 0%-3%.
In the method for the invention, the nonrestrictive example that can be used as the alpha-olefin of comonomer is propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 4,6-dimethyl-1-heptene, 1-decene, 1-dodecylene, tetradecene, cetene, vaccenic acid, eicosylene and allyl cyclohexane.
In the method for the invention, the nonrestrictive example that can be used as the cyclenes alkene of comonomer is cyclopentenes, tetrahydrobenzene and norbornylene.
Also can comprise by polyenoid deutero-unit according to multipolymer of the present invention.
The polyenoid that can be used as according to the comonomer of multipolymer of the present invention comprises following kind:
-can cyclopolymerization non-conjugated diene, for example, 1,5-hexadiene, 1,6-heptadiene and 2-methyl isophthalic acid, 5-hexadiene.
-the unitary diene of unsaturated monomer especially conjugated diolefine such as divinyl and isoprene can be provided, and linear non-conjugated diene such as trans 1,4-hexadiene, cis 1,4-hexadiene, 6-methyl isophthalic acid, 5-heptadiene, 3,7 dimethyl-1,6-octadiene and 11-methyl isophthalic acid, 10-12 carbon diene.
About except non-conjugated α-ω-diene, having the polyenoid of 6 or more carbon atoms, preferably use as second alpha-olefin comonomer with the amount of 0-3mol%.
Of the present inventionly make us interested embodiment especially and comprise ethene and 1-hexene or the multipolymer of high alpha-olefin more.
Multipolymer according to the present invention is characterised in that the extreme uniform distribution of comonomer on the polymer chain, and more precisely, is to comprise the fact of the unitary sequence of two or more continuous alpha-olefin of extremely low quantity.
In the multipolymer of the present invention, the analysis of the distribution of comonomer unit is adopted 13The C-NMR spectral method carries out.This mensuration is undertaken by the method that Randall is disclosed in " polymer chemistry physics " 1989,29,201.In ethene/1-hexene, the distribution of triad is calculated by following relational expression:
HHH＝T ββ????EHE＝T δδ???HHE＝T βδ????HEH＝S ββ??HEE＝S βδ
EEE＝0.5(S δδ+0.5?S γδ)
Wherein, EHE, HHE and HHH represent ethene in the multipolymer/1-hexene/ethene respectively, 1-hexene/1-hexene/ethene and 1-hexene/1-hexene/1-hexene sequence.As for the NMR nomenclature, consult J.Carmen, R.A.Harrington, C.E.Wilkes, polymer (Macromolecules), 10,537 (1977).Numerical value is normalization.The unitary number of isolated 1-hexene is many more on polymer chain, and the ratio of EHE/ (EHE+HHE+HHH) is more near 1.
The function of the 1-hexene quantity that the number of hexene sequence seemingly exists in the chain.
Table 2 and table 3 relate to ethene/1-hexene copolymer that the method according to this invention obtains.
Especially, in table 2, reported that in the presence of the metallocene complex of above-mentioned report, by ethene/1-hexene copolymer that method of the present invention obtains, the ratio of EHE/ (EHE+HHE+HHH) is the function of 1-hexene mole % in the chain.1-hexene element number is identical, and the ratio of the EHE/ of multipolymer of the present invention (EHE+HHE+HHH) is always than the numerical value height of the multipolymer that is obtained by the metallocene that is used for reference to embodiment.Reacted improved 1-hexene cell distribution in chain.
In multipolymer according to the present invention, reactivity ratio r 1R 2Product very low, r wherein 1Be the relative response speed of comonomer to ethene, r 2Be the relative response speed of ethene to comonomer.Especially, this product is usually less than 0.30, preferably is lower than 0.20, more preferably less than 0.15.Diad is by the triad distributed computation.
Under ethene/1-hexene situation, reactivity ratio r 1R 2Product according to being disclosed in J.Uozomi, K.Soga, Mak.Chemie, 193,823, the following formula of (1992) calculates:
r 1＝2EE/(EH)X
r 1R 2=4 (EE.HH)/EH 2, wherein
X=[E]/[H], monomer mole ratio in the polymerization bath.
Especially, ratio EHE/ (EHE+HHE+HHH) satisfies following relation:
EHE/(EHE+HHE+HHH)≥0.75
Preferably:
EHE/(EHE+HHE+HHH)≥0.85
More preferably
EHE/(EHE+HHE+HHH)≥0.9。
The inherent viscosity of multipolymer of the present invention (I.V.) preferably is higher than 1.0dl/g usually above 0.5dl/g.Limiting viscosity can reach the numerical value of 3.0dl/g, even higher.
The molecular weight of polymkeric substance can by change catalyst component kind or concentration, or use molecular weight regulator, such as hydrogen, change.
Usually, multipolymer of the present invention has narrow molecular weight distribution.Molecular weight distribution is by ratio M w/ M nExpression, for multipolymer of the present invention, when employed metallocene was pure isomer, this ratio preferably less than 3.5, was more preferably less than 3 usually less than 4.
Molecular weight distribution can change by mixture that adopts different metallocene complexes or the molecular weight regulator that carries out polymerization and/or different concns under different polymerization temperatures stage by stage.
Multipolymer of the present invention can pass through traditional hot plastic material working method (molding is extruded, injection etc.) and change the setting goods into.
Provide following embodiment to be used for illustrative purposes, and do not plan to limit the scope of the invention.
Common processes rules and feature
Use following abbreviation:
The THF=tetrahydrofuran (THF)
Et 2The O=ether
The NaOEt=sodium ethylate
The tBuOK=potassium tert.-butoxide
The DMSO=dimethyl sulfoxide (DMSO)
DMF=N, dinethylformamide
The BuLi=butyllithium
All nitrogen that operate in exist down, adopt traditional Schlenk-line technology to carry out.From blue sodium-benzophenone ketyl (ether), CaH 2(CH 2C 12), or distilling off solvent in the triisobutyl aluminium (hydrocarbon), in nitrogen, preserve.Butyllithium (Aldrich) directly uses.
The 1H-NMR of metallocene analyzes and carry out (CD on DPX 200 Bruker energy spectrometer 2C 12, and at the remaining CHDCl in 5.35ppm place 2The middle crest of triplet contrast, position).All NMR solvent Vanadium Pentoxide in FLAKES dryings, and distillation before use.Standard rare gas element technology is used in the preparation of sample, carries out in nitrogen atmosphere.Polymkeric substance 13C-NMR reaches 1H-NMR analyzes and carries out on Bruker DPX 400 energy spectrometeies, operates under 400.13MHz and 100.61MHz respectively.Sample is analyzed at 120 ℃ of solution with tetrachloro two deuterium ethane.
Limiting viscosity (I.V.) is measured in 1,2,3,4-tetralin at 135 ℃.
The fusing point of polymkeric substance (Tm) is measured by dsc (D.S.C.) on DSC Mettler instrument according to following method.The about 10 milligrams of samples that obtain in the auto-polymerization reaction are cooled to-25 ℃, use sweep velocity to be heated to 200 ℃ then corresponding to 20 ℃/min.Sample kept 5 minutes at 200 ℃, used the sweep velocity corresponding to 20 ℃/min to be cooled to 0 ℃ then.Then, use corresponding to the sweep velocity of 10 ℃/min and carry out second time scanning.The numerical value that is write down is the numerical value in scanning for the second time.
Molecular weight distribution is measured by GPC, and GPC carries out on WATERS 150 instruments in 135 ℃ of orthodichlorobenzenes.
The preparation of metallocene
Racemize-dichloride isopropylidene-two (3-sec.-propyl-indenyl) is closed zirconium (rac-CMe 2(3-iPr-Ind) 2ZrCl 2), racemize-dichloride isopropylidene-two (3-trimethylsilyl-indenyl) is closed zirconium (rac-CMe 2(3-Me 3Si-Ind) 2ZrCl 2), racemize-dichloride isopropylidene-two (3-methyl-indenyl) is closed zirconium (rac-CMe 2(3-Me-Ind) 2ZrCl 2), racemize-dichloride isopropylidene-two (the 3-tertiary butyl-indenyl) is closed zirconium (rac-CMe 2(3-tBu-Ind) 2ZrCl 2) synthetic undertaken by the method that is disclosed among the WO 96/22995.
Racemize-dichloride methylene radical-two (the 3-tertiary butyl-1-indenyl) is closed the synthetic of zirconium
(a) tertiary butyl-indenes is synthetic
42.0 gram indenes (technical grade, according to gas chromatographic analysis content 94%, 39.5 gram, 340 mmoles), 50%w potassium hydroxide aqueous solution (308 gram potassium hydroxide is dissolved in 308 ml waters) and be dissolved in 15.8 gram Adogen (Aldrich in 139.7 gram (1019.6 mmole) tert.-butyl bromides, 34 mmoles) in this order, at room temperature, add in the jacketed glass reactor of 1 liter of band mechanical stirring (B ü chi).Organic phase-change is green.Mixture heating up to 60 ℃, vigorous stirring 2 hours (observe pressure and be increased to 2.5bar-g) is cooled to room temperature then.The total overall reaction time is 3 hours.Organic phase technical grade hexane extraction (3 * 200mL), adopt gas chromatographic analysis.Conversion: the 3-tertiary butyl-indenes of 74.5%w and the 1-tertiary butyl-indenes of 1.8%, unreacted indenes 13.7%w.Solution is (rotation vacuum) evaporation under the decompression situation, and the dark rice-pudding look of gained thick liquid distills under 1mmHg, is collected in 70 ℃-80 ℃ cut (40 grams, the 3-tertiary butyl-indenes of 76.8% and the 1-tertiary butyl-indenes of 19.5%, no indenes).
(b) two (the 3-tertiary butyl-indenyl) methane is synthetic
In three mouthfuls of 1 liter of flasks of band stirring rod, add in the following order: 10.32 gram tBuOK (92 mmole), 400 milliliters of DMF, 80.6 gram tertiary butyl indenes is (according to gas-chromatography 98.2%, 460 mmoles), reach 18.6 milliliters of formlinata aquae concentratacs (37%, 6.9 gram, 230 mmoles), dropwising above 15 minutes.Observe gentle thermopositive reaction, solution reddens.Mixture is stirring at room 2 hours, suddenly in the mixture by impouring ice and ammonium chloride stops reaction, and (2 * 250mL) extractions, decompression concentrate down to obtain the orange oily product that following G.C. forms: 1-tertiary butyl indenes, 0.3% with ether; 3-tertiary butyl indenes, 2.8%; Target product, 78.3%; All the other are by product.Crude product output: 83.6 grams, phase product yield 79.9%.Orange oily product leaves standstill crystallization (about 1 hour).Product is further purified with the pentane washing, and two (the 1-tertiary butyl-3-indenyl) methane stays as pale yellow powder, by G.C purity 99.8%.
(c) dichloride methylene radical-two (the 3-tertiary butyls-1-indenes) close the synthetic of zirconium
Pure two (the 1-tertiary butyl-3-indenyl) methane (30.9mmol) of 11.0 grams are dissolved in the 250mLSchlenk pipe in the 200mL ether, and solution is cooled to-15 ℃.40ml, the n-buli hexane solution of 1.6M (63.3mmol) under agitation dropwises at 15min.Solution can be warming up to room temperature, stirs 4.5 hours.Turbidity increases gradually, finally forms the yellow suspension thing.7.2 gram ZrCl 4(30.9mmol) in the 200mL pentane, form slurry.Two kinds of mixtures all are cooled to-80 ℃, and the lithium salt solution in the ether is added to the ZrCl in the pentane fast 4Slurry.Remove cooling bath.After 20 minutes, slurry color changes redness into by yellow.Reaction mixture at room temperature stirs and spends the night drying under reduced pressure.Red powder is made slurry in the 200mL pentane, transfer in the filtering apparatus, these instrument and equipment have more than the sintered glass and below be connected to system side arm (refluxing), bottom to allow solution accept flask and top spherical condensation tube.Red solid is used backflow pentane extracting 3.5 hours.The filtrate evaporated under reduced pressure drying obtaining comprising the red mashed prod of racemize-methylene radical-two (3-tertiary butyl-1-indenyl) zirconium dichloride that does not contain its mesoisomer, but comprises the polymkeric substance byproduct.Mashed prod obtains 1 gram pure products with ether (20+10mL) washing 2 times.Red solid on the sintered glass is further used the methylene dichloride extracting, is greenish orange look (6 hours) and dry up to filtrate.1H-NMR shows that pure racemize-dichloride methylene radical-two (the 3-tertiary butyl-indenyls) close exist (7.25 gram) of zirconium.The overall yield that racemize-dichloride methylene radical-two (the 3-tertiary butyl-indenyl) is closed zirconium (8.25 gram red powder) is 52%. 1H-NMR(CDCl 3，d，ppm)：s，1.41，tBu，18H；s，4.78，CH 2，2H；s，5.79，2H，Cp-H；m，7.15，2H，m，7.36，2H；m，7.47，2H；m，7.78，2H.
Dichloride methylene radical-two (3-sec.-propyl-1-indenyl) closes the synthetic of zirconium
(a) 3-sec.-propyl-1-indenes is synthetic
To dissolve in 25 gram indenes (Aldrich, 94.4%) of 140mL ether, insert in the 0.5L flask, be cooled to-20 ℃; Dripped at about 30 minutes the 141mL n-Butyl Lithium (the 1.6M hexane solution, 226mmoL).Reaction mixture allows to rise to room temperature, stirs 5 hours (terra-cotta solution) then.This solution slowly adds the 140mL ether that remains on 0 ℃ and 101mL isopropyl bromide (i-PrBr), and (density 1.31g/ml is in solution 1.07mol) for Aldrich, MW 123g/mol.Reaction was under agitation carried out 72 hours in room temperature.After 24 hours, take out aliquots containig and carry out gas chromatographic analysis (indenes=12.1%, sec.-propyl indenes=56.5%, two sec.-propyl indenes=18.8%), (indenes=4.6%, sec.-propyl indenes=66.8% after 48 hours, two sec.-propyl indenes=16.5%), (indenes=4.8%, sec.-propyl indenes=65.3%, two sec.-propyl indenes=16.8%) at last.Mixture impouring 300 gram on ice, (3 * 200mL) extractions, ethereal extract mixes with organic layer water layer, uses dried over mgso, vacuumizes after the filtration to obtain 30.9 except that desolvating and restrain yellow oil with ether.(based on gas chromatographic analysis, productive rate 62%).Distillation 18 gram these oily matter (adding granular NaOH in case polymerization has the 20cm Vigreux column) are collected cut 10 grams under the 95-105 ℃ of 10mmHg, GC: sec.-propyl indenes (2 isomer)=92.1%, two sec.-propyl indenes=6.7%. 1H-NMR(CDCl 3，d，ppm)：d，1.45，1，47，6H；m，3.47，CH，1H；s，3.47，2H，CH 2；s，6.35，1H；m，7.47，2H；m，7.3-7.7，4H。Main isomer is a 3-sec.-propyl indenes.
(b) two (3-sec.-propyl-indenyl) methane is synthetic
In three mouthful of 500 ml flasks of band stirring rod, add in the following order: 10 grams dissolve in 250mLDMSO the sec.-propyl indenes (92%, molecular weight 158,58.3mmol), and 1.42 gram t-BuOK (molecular weight 112.82,12.6mmol), it is green that yellow solution turns.Added at 15 minutes 70mL DMSO the 2.56mL formlinata aquae concentratac (37%, molecular weight 30.03,31.6mmol).Observe gentle thermopositive reaction, solution becomes burgundy.After adding, reaction mixture is stirring at room 16 hours, stops reaction by the impouring 200 gram ice and the mixture of 0.3 gram ammonium chloride are sudden.(2 * 250mL) extraction organic products, (3 * 100mL) washings mix organic layer to water layer, use dried over mgso, filter and concentrate, and obtain 13.65 gram yellow oil, analyze this oily matter through GC and comprise 32% required product with ether with ether.
(c) dichloride methylene radical-two (3-sec.-propyls-1-indenes) close the synthetic of zirconium
Thick two (3-sec.-propyl-1-indenyl) methane of 13.6 grams are dissolved in the 250mL ether in 250mL Schlenk pipe, and solution is cooled to-80 ℃.With 33.3ml, the n-buli hexane solution of 2.5M (83.2mmol) is under agitation dropwising above 15min.Solution can be warming up to room temperature, stirs 5 hours.Turbidity increases gradually, finally forms orange-yellow throw out.Under vacuum, remove ether, add 200mL toluene.9.7 gram ZrCl 4(molecular weight 233.03 41.62mmol) forms slurry in 200mL toluene.Two kinds of mixtures all are cooled to-80 ℃, the ZrCl in the toluene 4Slurry is added to the lithium salt solution in the toluene fast.Remove cooling bath.Reaction mixture at room temperature stirs and spends the night.Filter: residue is thickness colloid (removing).Decompression filtrate down is evaporated to 25mL: filter and obtain solid sediment: 1H-NMR (CD 2Cl 2, d, ppm): 92% mesomeride; Ps-t, 1.31, sec.-propyl, 12H; Quintet, 3.32, CH, 2H; Quartet, 4.84,4.91,5.01,5.08,2H, CH 2-bridging; S, 5.81,2H, Cp-H; T, 6.9-7.0,2H; T, 7.06-7.15,2H; M, 7.47-7.55,4H.Consult Fig. 2.
The filtrate drying obtains red sticky solid (5.8 gram), and this solid dispersed is in 30mL ether and 2mL methylene dichloride, 0 ℃ of filtration.Dried residue obtains 1 gram red powder. 1H-NMR shows that chemical pure dichloride methylene radical-two (3-sec.-propyl-indenyls) close exist (80% racemic modification, 20% mesomeride) of zirconium. 1H-NMR (CD 2Cl 2, d, ppm): d, 1.17,1.21, CH 3, 6H; D, 1.31,1.34, CH 3, 6H; Quintet, 3.13-3.20, CH, 2H; S, 4.82,2H, CH 2-bridging; S, 5.78,2H, Cp-H; T, 7.07-7.13,2H; T, 7.25-7.30,2H; D, 7.47-7.52,2H; D, 7.60-7.65,2H.
Dichloride methylene radical-two (3-trimethylsilyl-1-indenyl) closes the synthetic of zirconium
(a) two (1-trimethylsilyl-3-indenyl) methane is synthetic
With 9.56 grams, be dissolved in the 70mL ether in 250mL Schlenk pipe by resulting two (1-indenyl) methane (39.1mmol) of synthetic 10 reports, solution is cooled to-78 ℃.33.0ml the n-buli hexane solution of 2.5M (82.5mmol) is under agitation dropwising above 30min.Gained solution can be warming up to room temperature, stirs 3 hours, obtains the slight turbid solution of brownish black.(82.7mmol) dissolves in the 50mL ether with the 10.5mL trimethylchlorosilane.Two kinds of mixtures all are cooled to-78 ℃, are surpassing 20 minutes, and the lithium salt solution of ether joins the diethyl ether solution of trimethylchlorosilane; Solution is by the brown brown that changes into.Remove cooling bath, reaction mixture at room temperature stirs and spends the night.After 20 hours, the solution that becomes limpid a little reacts with several milliliters of sudden the stopping of MeOH, filters also to concentrate, and obtains two (1-trimethylsilyl-3-indenyl) methane (productive rate 74.2%, mesomeride/racemic modification=1/1) of 11.28 gram brownish blacks.
1H-NMR (CDCl 3, δ, ppm) :-0.04-0.03 (s, 18H, CH 3); 3.35-3.45 (m, 2H, CH or CH 2Bridging); 3.93-4.00 (bs, 2H, CH 2Bridging or CH); 6.30-6.40 (m, 2H, Cp-H); 7.10-7.50 (m, 8H).
(b) dichloride methylene radical-two (3-trimethylsilyls-1-indenes) close zirconium, CH 2(3-Me 3Si-Ind) 2ZrCl 2, synthetic
With 4.90 grams, be dissolved in the 70mL ether in 250mL Schlenk pipe by resulting two (1-trimethylsilyl-3-indenyl) methane (12.6mmol) of above-mentioned report, solution is cooled to-70 ℃.10.6ml the n-buli hexane solution of 2.5M (26.5mmol) under agitation splashes into.Gained solution can be warming up to room temperature, stirs 3 hours.Turbidity increases, and finally forms brown black suspension liquid.2.94 gram ZrCl 4(12.6mmol) in the 50mL pentane, form slurry.Two kinds of mixtures all are cooled to-70 ℃, and the diethyl ether solution of lithium salts is added to ZrCl fast 4The pentane slurry; Remove cooling bath.Reaction mixture at room temperature stirs and spends the night.After the filtration, the concentrating residues thing is also used the toluene extracting, obtains pink powder. 1H-NMR analyzes and shows CH 2(3-Me 3Si-1-Ind) 2ZrCl 2Mesomeride/racemic modification exist with 75/25.Dried filtrate obtains the brownish black sticky solid, adds pentane; The gained mixture filters then stirring at room 1 hour.The final drying residue obtains 1.87 gram orange powders. 1H-NMR analyzes and shows CH 2(3-Me 3Si-1-Ind) 2ZrCl 2Racemic modification/mesomeride have (yield 27.0%) with 81/19.
1H-NMR (CD 2Cl 2, δ, ppm): 0.22 (s, 6H, CH 3); 0.34 (s, 6H, CH 3); 4.79 (s, CH 2Bridging, 2H); 4.93 (q, CH 2Bridging, 2H); 6.47 (s, Cp-H, 2H); 6.57 (5, Cp-H, 2H); 7.06-7.72 (m, 16H).
Polyreaction
Methyl oxidation aluminum alkyls (MAO)
Its commercially available 10% toluene solution (Witco) is dry under vacuum, until obtaining solid glass shape material; Fine ground and further vacuum-treat up to removing all volatilizable things (4-6 hour, 0.1mmHg, 50 ℃), obtains white free flowing powder.
Three (2,4,4-trimethylammonium-amyl group) aluminium (TIOA)
Employed its commercially available sample (Witco) dilutes in specified solvent, obtains 1M solution.
Embodiment 1
Ethene/1-hervene copolymer reaction
Have magnetic stirring apparatus, the 200mL glass autoclave of temperature indicator and ethene feeder sleeve feeds ethene down at 35 ℃ and purifies.At room temperature add 90mL heptane and 10mL1-hexene.Catalyst system is by adding MAO toluene solution and the 0.1mg (2.04 * 10 that 0.22mL concentration is 1M continuously at the 10mL heptane -6Mol) dichloride methylene radical-two (the 3-sec.-propyls-1-indenyl) that are dissolved in a small amount of as far as possible toluene close zirconium and prepare separately.Stir after 5 minutes, solution adds and to be in the autoclave that ethylene gas flows down, and the off-response device is warming up to 70 ℃, makes reactor pressure rise to 4.5bar with ethene.By adding ethene, total pressure remains unchanged.After 15 minutes, by to reactor cooling, degasification and add 1ml methyl alcohol and stop polyreaction.Product cleans with acidic methanol, uses washed with methanol then, and is dry in baking oven in 60 ℃ under vacuum at last.Output is 3.59 grams, and corresponding activity is 769.3Kg/gZr.h.Polymer property viscosity is 1.22dl/g.
The characteristic of gained multipolymer is shown in table 2.
Embodiment 2
Repeat embodiment 1, not existing together is, adds the 5mL1-hexene, rather than the 10mL1-hexene.
Polymerizing condition is illustrated in the table 1.
The characteristic of gained multipolymer is shown in table 2.
Embodiment 3
Repeat embodiment 1, not existing together is, uses 0.27 mmole TIOA/H 2O (Al/H 2The O mol ratio is 2.11), rather than MAO.Output is 0.73 gram, and corresponding activity is 123.2Kg/gZr.h.Polymer property viscosity is 2.58dl/g.
Polymerizing condition is illustrated in the table 1.
The characteristic of gained multipolymer is shown in table 2.
Embodiment 4
Repeat embodiment 1, only be to use 9: 1 mixtures of 0.22 mmole TIOA-O/MAO.Work as Al/H 2The O mol ratio is 2.07 o'clock, obtains TIOA-O.
Polymerizing condition is illustrated in the table 1.
The characteristic of gained multipolymer is shown in table 2.
Embodiment 5
Repeat embodiment 1, not existing together is, uses 0.12mg dichloride isopropylidene-two (3-sec.-propyl-indenyls) to close zirconium and 0.24 mmole MAO.
Polymerizing condition is illustrated in the table 1.
The characteristic of gained multipolymer is shown in table 2.
Embodiment 6
Repeat embodiment 1, only be to use 0.12mg dichloride isopropylidene-two (3-sec.-propyl-indenyls) to close 9: 1 mixtures of zirconium and 0.24 mmole TIOA-O/MAO.Obtain TIOA-O, Al/H 2The O mol ratio is 2.07.
Polymerizing condition is illustrated in the table 1.
The characteristic of gained multipolymer is shown in table 2.
Embodiment 7
Repeat embodiment 1, not existing together is, uses 0.2mg dichloride methylene radical-two (3-trimethylsilyl-indenyls) to close zirconium.
Polymerizing condition is illustrated in the table 1.
The characteristic of gained multipolymer is shown in table 2.
Embodiment 8
Repeat embodiment 1, only be to use 0.1mg dichloride isopropylidene-two (3-methyl-indenyls) to close zirconium and 0.23 mmole TIOA/H 2O (Al/H 2The O mol ratio is 2.07), do not use MAO.
Polymerizing condition is illustrated in the table 1.
The characteristic of gained multipolymer is shown in table 2.
Embodiment 9
Repeat embodiment 1, not existing together is, uses 0.12mg dichloride isopropylidene-two (3-trimethylsilyl-indenyls) to close zirconium.
Polymerizing condition is illustrated in the table 1.
The characteristic of gained multipolymer is shown in table 2.
Embodiment 10
The copolyreaction of ethene/1-octene
Have magnetic stirring apparatus, the 260mL glass autoclave of temperature indicator and ethene feeder sleeve feeds ethene down at 35 ℃ and purifies.At room temperature add 86mL heptane and 4.1mL through LiAlH 4Distilled 1-octene.Catalyst system adds the metallocene that MAO (0.21 mmole, the toluene solution of 1M) and 0.1mg (0.000205mg zirconium) be dissolved in the embodiment 1 in the toluene (consumption is the least possible) by order and prepares.Stir after 5 minutes, solution is diluted to 10mL with heptane, and the solution adding is in the autoclave that ethylene gas flows down, and the off-response device is warming up to 70 ℃, and pressure rises to 4bar.By adding ethene, total pressure remained unchanged 20 minutes.By to reactor cooling, degasification and add 1ml methyl alcohol and stop polyreaction.Resulting polymers cleans with acidic methanol, uses washed with methanol then, and is dry in baking oven in 60 ℃ under vacuum at last.Obtain the polymkeric substance (270Kg/gZr/h) that 1.68 grams have following characteristics: I.V.=1.82dL/g; 1-octene=5.73mol%, Tm=92.5 ℃; Δ H=63J/g; The molecular fraction that triad distributes: [EXE]=5.73; [XXX]=0; [XXE]=0; [EXE]/X Tot=1.Wherein X represents the 1-octene.
Embodiment 11
The polyreaction of ethene/1-decene
Have magnetic stirring apparatus, the 200mL glass autoclave of temperature indicator and ethene feeder sleeve feeds ethene down at 35 ℃ and purifies.At room temperature add 85mL heptane and 5mL through the distilled 1-decene of LiAlH4.Catalyst system adds the metallocene that MAO (0.22 mmole, the toluene solution of 1M) and 0.1mg (0.000205mg zirconium) be dissolved in the embodiment 1 in the toluene (consumption is the least possible) by order and prepares.Stir after 5 minutes, solution is diluted to 10mL with heptane, and the solution adding is in the autoclave that ethylene gas flows down, and the off-response device is warming up to 70 ℃, and pressure rises to 4bar.By adding ethene, total pressure remained unchanged 10 minutes.By to reactor cooling, degasification and add 1ml methyl alcohol and stop polyreaction.Resulting polymers cleans with acidic methanol, uses washed with methanol then, and is dry in baking oven in 60 ℃ under vacuum at last.Obtain the polymkeric substance (1045Kg/gZr/h) that 3.2 grams have following characteristics: I.V.=2.01dL/g; 1-decene=7.48mol%, Tm=72.8 ℃; Δ H=63J/g; The molecular fraction that triad distributes: [EXE]=7.48; [XXX]=O; [XXE]=O; [EXE]/X Tot=1.Wherein X represents 1-decene.
Embodiment 12 (reference example)
Repeat embodiment 1, only be to use racemize-dichloride methylene radical-two (the 3-tertiary butyl-indenyls) to close zirconium.
Polymerizing condition is illustrated in the table 1.
The characteristic of gained multipolymer is shown in table 2.
Embodiment 13 (reference example)
Repeat embodiment 1, only be to use 0.3mg racemize-dichloride isopropylidene-two (the 3-tertiary butyl-indenyls) to close zirconium, 1.15 mmole TIOA/H 2O (Al/H 2The O mol ratio is 4.18) and the 15mL1-hexene.
Polymerizing condition is illustrated in the table 1.
The characteristic of gained multipolymer is shown in table 2.
Embodiment 14 (reference example)
Repeat embodiment 1, only be to use racemize-dichloride isopropylidene two indenyls to close zirconium.
Polymerizing condition is illustrated in the table 1.
The characteristic of gained multipolymer is shown in table 2.
Embodiment 15 (reference example)
Repeat embodiment 1, only be to use racemize-dichloride methylene radical two indenyls to close zirconium.
Polymerizing condition is illustrated in the table 1.
The characteristic of gained multipolymer is shown in table 2.
Table 1
Embodiment Zirconocene dichloride Aluminium/zirconium The 1-hexene Time (min) Output (g) Activity (Kg/g zr/h)
?1 ??CH 2(3-iPr-Ind) 2 ?0.1 ????1000 ????10 ????15 ????3.59 ????769.3
?2 ??“ ?0.1 ????1000 ????5 ????10 ????4.12 ????1324.4
?3 ??“ ?0.1 ????1000 ????5 ????15 ????0.73 ????123.2
?4 ??“ ?0.1 ????1000 ????5 ????10 ????1.43 ????460
?5 ??CMe 2(3-iPr-Ind) 2 ?0.1 ????1000 ????5 ????10 ????3.01 ????852.6
?6 ??“ ?0.1 ????1000 ????10 ????15 ????0.67 ????126.5
?7 ??CH 2(3-Me 3Si-Ind) 2 ?0.2 ????1000 ????10 ????15 ????1.96 ????236
?8 ??CMe 2(3-Me-Ind) 2 ?0.1 ????1000 ????10 ????10 ????6 ????1818.0
?9 ??CMe 2(3-Me 3Si-Ind) 2 ?0.1 ????1000 ????10 ????10 ????1.38 ????436.4
12 (reference examples) ??CH 2(3-tBu-Ind) 2 ?0.1 ????1000 ????10 ????10 ????1 ????339.9
13 (reference examples) ??CMe 2(3-tBu-Ind) 2 ?0.3 ????2000 ????15 ????20 ????0.67 ????40.0
14 (reference examples) ??CMe 2(Ind) 2 ?0.1 ????1000 ????10 ????15 ????2.28 ????297.6
15 (reference examples) ??CH 2(Ind) 2 ?0.1 ????1000 ????10 ????15 ????1.68 ????295.0
Table 2
Embodiment Zirconocene dichloride ??1-hcxcne ??(％mols) ??????????????????????N.M.R. ??r 1 r 1·r 2 ??I.V. ??(dl/g) ??Tm ??(℃) ??ΔH ??(J/g)
????EHE???????????HHH??????????HHE ??????????????(％mols) ????EHE/ (EHE+HHE+HHH
?1 ???CH 2(3-iPr-Ind) 2 ????17.86 ??16.8 ????0 ????1.06 ????0.94 ??6.41 ??0.113 ??1.22 ??n.d.# ??n.d.#
?2 ???“ ????12.35 ??11.98 ????0 ????0.37 ????0.97 ??5.2 ??0.091 ??1.61 ??57.5 ??29
?3 ???“ ????6.91 ??6.91 ????0 ????0 ????1 ??10.0 ??n.d ??2.58 ??74.8 ??58
?4 ???“ ????7.27 ??7.27 ????0 ????0 ????1 ??9.83 ??n.d. ??2.49 ??76.0 ??65.9
?5 ???CMe 2(3-iPr-Ind) 2 ????9 ??9 ????0 ????0 ????1 ??7.36 ??n.d ??2.1 ??73 ??52
?6 ???“ ????11.24 ??10.8 ????0 ????0.44 ????0.96 ??12.26 ??0.142 ??2.8 ??63.4 ??43.1
?7 ???CH 2(3-Me 3Si-Ind) 2 ????10.09 ??8.73 ????0 ????1.36 ????0.87 ??14.9 ??0.627 ??0.81 ??77.5 ??53.2
?8 ???CMe 3(3-Me-Ind) 2 ????18.41 ??17.6 ????0.22 ????0.59 ????0.96 ??6.25 ??0.105 ??0.5 ??44.7 ??5
?9 ???CMe 2(3-Me 3Si-Ind) 2 ????8.78 ??7.8 ????0 ????0.98 ????0.89 ??16.1 ??0.52 ??1.29 ??76 ??51
12 (reference examples) ???CH 2(3-tBu-Ind) 2 ????5.01 ??3.66 ????0 ????1.35 ????0.73 ??35.6 ??3.160 ??2.59 ??98.6 ??99.9
13 (reference examples) ???CMe 2(3-tBu-Ind) 2 ????8.16 ??5.92 ????0.21 ????2.03 ????0.73 ??32.4 ??2.193 ??1.36 ??88.3 ??79.4
14 (reference examples) ???CMe 2(Ind) 2ZrCl 2 ????24.0 ??18.7 ????1.66 ????4.18 ????0.76 ??5.04 ??0.559 ??0.18 ??oil
15 (reference examples) ???CH 2(Ind) 2ZrCl 2 ????26.56 ??20.06 ????1.32 ????5.17 ????0.76 ??3.71 ??0.362 ??0.14 ??oil
# scans Tm=48 ° for the first time, Δ H=3.8 J/g; N.d.=can not measure, because the HH sequence does not exist

Claims (16)

1. method for preparing ethylene copolymer, this method are included in catalyzer and have down that ethene reaches randomly one or more polyenoid polyreactions with at least a alpha-olefin, and catalyzer is contacted with (B) by (A) and obtains:
(A) general formula is the metallocene complex of (I):
Wherein:
Substituent R 1Be hydrogen atom or C 1-C 20Alkyl;
Substituent R 2Be CHR 10R 11, SiR 12R 13R 14Or GeR 15R 16R 17Group,
Wherein: R 10, R 11, R 12, R 15Be hydrogen atom, C 1-C 20Alkyl, C 3-C 20Cycloalkyl, C 2-C 20Alkenyl, C 6-C 20Aryl, C 7-C 20Alkaryl or C 7-C 20Arylalkyl radical, optional Siliciumatom or the germanium atom of comprising;
R 13, R 14, R 16, R 17Be C 1-C 20Alkyl, C 3-C 20Cycloalkyl, C 2-C 20Alkenyl, C 6-C 20Aryl, C 7-C 20Alkaryl or C 7-C 20Arylalkyl radical, optional Siliciumatom or the germanium atom of comprising;
R 3And R 4, identical or different, be hydrogen atom or-CHR 5R 6Group;
R 3And R 4Can form and to contain heteroatomic, as to have 3-8 carbon atom ring;
R 5And R 6, identical or different, be hydrogen atom, C 1-C 20Alkyl, C 3-C 20Cycloalkyl, C 2-C 20Alkenyl, C 6-C 20Aryl, C 7-C 20Alkaryl or C 7-C 20Arylalkyl radical, it can form can contain heteroatomic, as to have 3-8 carbon atom ring;
R 7Substituting group, identical or different, be C 1-C 20Alkyl, C 3-C 20Cycloalkyl, C 2-C 20Alkenyl, C 6-C 20Aryl, C 7-C 20Alkaryl or C 7-C 20Arylalkyl radical, optional Siliciumatom or the germanium atom of comprising; And optional two adjacent R 7Substituting group can form the ring that comprises 5-8 carbon atom, and n is the integer of 0-4;
M is selected from that those belong to 3,4 in the periodic table of elements (IUPAC redaction), the transition metal atoms of 5,6 families or group of the lanthanides or actinium series, and X, identical or different, be the single anion ligand, such as hydrogen atom, halogen atom, R 8, OR 8, OSO 2CF 3, OCOR 8, SR 8, NR 8 2Or PR 8 2Base, wherein, substituent R 8Be C 1-C 20Alkyl, C 3-C 20Cycloalkyl, C 2-C 20Alkenyl, C 6-C 20Aryl, C 7-C 20Alkaryl or C 7-C 20Arylalkyl radical, optional Siliciumatom or the germanium atom of comprising;
P is the integer of 0-3, and the oxidation state that equals metal M deducts 2; And
(B) can form the oxidation of alkyl aluminium and/or the title complex of alkyl metallocene cation.
2. the process of claim 1 wherein that described oxidation of alkyl aluminium is by being AlR with water and general formula 9 3Or Al 2R 9 6Organo-aluminium compound contact and obtain, wherein the R9 substituting group is same to each other or different to each other, definition and R 1Identical.
3. the process of claim 1 wherein that the mol ratio of aluminium and water was 1: 1 to 100: 1 scope.
4. the method for any one among the claim 1-3, wherein said oxidation of alkyl aluminium is MAO, TIBAO and TIOAO, so-called organo-aluminium compound is TIOA, TMA and/or TIBA.
5. the process of claim 1 wherein that the compound that can form the alkyl metallocene cation is that general formula is Y +Z -Compound, Y wherein +Be protonic acid, can supply with a proton and with general formula (I) in the substituent X generation irreversible reaction of metallocene; Z -Be compatible negatively charged ion, this negatively charged ion does not have coordination, and can stablize the active catalyst form that is generated by two kinds of compound reactions, and this anionic unstable is enough to remove from Olefins matrix.
6. the method for claim 5, wherein negatively charged ion Z -Comprise one or more boron atoms
7. the method for any one among the claim 1-6, transition metal M is selected from titanium, zirconium and hafnium in the metallocene complex of its formula of (I).
8. the method for any one among the claim 1-7, substituent R in the metallocene complex of its formula of (I) 1And R 7It is hydrogen atom.
9. the method for claim 8, substituent R 2 is carbon atom, Siliciumatom or the germanium atoms that replace with two alkyl, cycloalkyl, aryl, alkaryl or aralkyl with 1-10 carbon atom in the metallocene complex of its formula of (I).
10. the method for any one among the claim 1-9, substituent X is chlorine atom or methyl in the metallocene complex of its formula of (I).
11. the method for any one among the claim 1-10, the metallocene complex of its formula of (I) are dichloride methylene radical-two (3-sec.-propyl-indenyls) closes zirconium or dichloride isopropylidene-two (3-sec.-propyl-indenyls) close zirconium.
12. the method for any one among the claim 1-11, wherein said method is carried out under the pressure range of-100-+100 ℃ temperature range and 0.5-100 crust.
13. the method for any one among the claim 1-12, wherein the mol ratio between the metal is 10: 1 to 20000: 1 in aluminium and the metallocene complex.
14. the method for any one among the claim 1-13, wherein alpha-olefin is selected from propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, decene and 1-dodecylene.
15. the method for any one among the claim 1-14, wherein alpha-olefin is the 1-hexene.
16. the method for any one among the claim 1-15, wherein said method are used for the preparation of the homopolymer and the multipolymer of ethene.
CN99800985A 1998-04-21 1999-04-13 Process for preparation of copolymers of ethylene with alpha-olefins Pending CN1272852A (en)

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